CN106423167A - Double transition metal based carbonized silkworm excrement catalyst and preparation method thereof - Google Patents
Double transition metal based carbonized silkworm excrement catalyst and preparation method thereof Download PDFInfo
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- CN106423167A CN106423167A CN201610812004.9A CN201610812004A CN106423167A CN 106423167 A CN106423167 A CN 106423167A CN 201610812004 A CN201610812004 A CN 201610812004A CN 106423167 A CN106423167 A CN 106423167A
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- 241000255789 Bombyx mori Species 0.000 title claims abstract description 79
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 52
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000003763 carbonization Methods 0.000 claims abstract description 64
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 238000010926 purge Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000009938 salting Methods 0.000 claims description 9
- 230000015556 catabolic process Effects 0.000 claims description 7
- 238000006731 degradation reaction Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000005416 organic matter Substances 0.000 claims description 5
- -1 transition metal salt Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005255 carburizing Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 238000010438 heat treatment Methods 0.000 abstract description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 1
- 230000005855 radiation Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 210000003608 fece Anatomy 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000004083 survival effect Effects 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/864—Cobalt and chromium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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Abstract
The invention discloses a double transition metal based carbonized silkworm excrement catalyst and a preparation method thereof. The preparation method comprises the following steps: (1) placing silkworm excrement in a high-temperature tube furnace, introducing protective gas to carry out purging, heating to 500-1000 DEG C, and carrying out high-temperature carbonization reaction to obtain carbonized silkworm excrement CS; (2) placing the CS in N2 atmosphere with concentration of H2 being 10-30 percent (by a volume ratio), and roasting the CS at the temperature of 200-500 DEG C to obtain the carbonized silkworm excrement HCS with low oxygen content; (3) impregnating the HCS in a saline solution of two transition metals, drying, and loading the transition metals on the carbonized silkworm excrement in a mode of plasma radiation; and (4) roasting the material at the temperature of 150-500 DEG C, thus finally obtaining the double transition metal based carbonized silkworm excrement catalyst. According to the double transition metal based carbonized silkworm excrement catalyst and the preparation method, the double transition metal based catalytic material is low in cost and can weaken influence of vapour to VOCs catalytic performance.
Description
Technical field
The invention belongs to volatile organic matter Treatment process field, it is related to the system of VOC oxidation catalyst
Preparation Method.
Background technology
20th century, human industry's civilization achieved unprecedented achievement, but earth environment for the survival of mankind also meets with
It is subject to unprecedented destruction.Environmental problem is just seriously threaten the survival and development of the mankind and is becoming global concern
First of ten big problems.The development of human society, starts to focus more on greatly with progressive after the primary demand meeting human survival
The pollution problem in compression ring border, the indoor environmental pollution that especially we depend on for existence has also become that 21 century people are most concerned to be asked
One of topic.
At present, lead in environmental pollution and destroyed factor various, volatile organic matter (VOCs) has become air
One important source of pollution (indoor and outdoor).Wherein, aldehydes VOCs (using formaldehyde based on) is as an industrial conventional class chemistry
Auxiliary agent, is widely present in various industrial processes and penetrates among everyday environments.The toxic action of aldehydes is very big, that is,
Make under low concentration (<0.1mg/m3) Long Term Contact also can damage human nerve maincenter and immune system, ground by international cancer
Study carefully structure I ARC and be classified as the first carcinogenic substance, give people class health and bring great threat.In addition, aldehydes VOCs also has high light
Learn reactivity, easy and ozone and NOx occur photochemical reaction, form the secondary pollution based on fine grained, thus becoming one
Class important as precursors thing plays key effect in compound atmosphere pollution forming process.Therefore, aldehydes VOCs has become a class spy
Do not merit attention and need one of VOCs object of priority acccess control, administer aldehydes VOCs pollution extremely urgent.
Production by Catalytic Combustion Process is a kind of one of effective technology administering VOC pollution.But when in organic exhaust gas
When concentration is very low, only rely on the temperature that reaction heat would become hard to maintain required in course of reaction, then be accomplished by addition supplementing one
Partial heat energy.Application adsoption catalysis burning complex art is a kind of proper selection in this case.Adsoption catalysis is fired
Burning complex art is by absorption and catalysis burning both process combination, such that it is able to form new cleaning system.This skill
Art is suitable for processing low concentration, the waste gas of Wind Volume.
Facing the urgent outstanding problem solving at present is, because the presence of vapor can lead to urge in actual condition
The degradation efficiency drastically declining and affecting of agent activity, therefore, research and a high activity are simultaneously but also with high hydrophobic
Non-precious metal catalyst, this has very important significance for administering the pollution under south China wet environment.
The technology of research efficient catalysis burning pollution administration, especially can be under higher levels of humidity working condition, efficiently
Catalytic oxidation technologies seem extremely important and urgent.And in catalytic combustion technology, efficient catalyst is core, therefore study
The impact to catalyst activity for the vapor and mechanism have important scientific meaning and actual application value.Persson etc. uses
Infusion process is prepared for catalyst, have studied the impact that vapor is catalyzed burning first activity to it.Result of study finds：In temperature
For when, when in reaction system, water vapor concentration increases to, catalyst burn first burn conversion ratio from drop to left and right, conversion
Rate have dropped.The catalyst that Kikuchi etc. is prepared with infusion process, for first institute is carried out with catalytic oxidation, research finds
The presence of vapor has obvious negative effect to the catalysis activity of these three catalyst, and wherein catalyst is subject to vapor
Impact is maximum, and the conversion ratio that first is burnt on a catalyst drastically declines.
Content of the invention
A kind of pair of transition metal base carbonization silkworm excrement catalyst it is characterised in that：Described double transition metal base carbonization silkworm excrements
The oxygen content of the catalyst carrier carbonization silkworm excrement of catalyst<8.0wt%, the content summation of transition metal is in 5-15wt%；Described
Double transition metal base carbonization silkworm excrement catalyst, the BET specific surface area having be 400-650m2/g；Low concentration (<800ppm)
VOCs and relative humidity be more than 50% when, VOCs degradation rate is reached with temperature T when 90%90<300℃.
The preparation method of double transition metal base carbonization silkworm excrement catalyst of the present invention, comprises the steps,
(1) preparation of carbonization silkworm excrement：Silkworm excrement is placed in high temperature process furnances, after logical protective gas purging, according to 2～8 DEG C/
The heating rate of min be heated to 500～1000 DEG C carry out high temperature cabonization reaction obtain carbonization silkworm excrement, be designated as CS.
(2) H of carbonization silkworm excrement2Deoxidation treatment：CS is placed in 10-30% (volume ratio) H2N2At 200-500 DEG C under atmosphere
Roasting 1-5h obtains low oxygen containing carbonization silkworm excrement HCS；
(3) HCS be impregnated in the salting liquid of two kinds of transition metal, will by way of plasma resonance after drying
Transition metal loads on carbonization silkworm excrement, prepared MxM1-x-HCS1；
(4) roasting of catalyst：MxM1-x-HCS1Roasting at 150-500 DEG C, finally obtains double transition metal base carbonization silkworms
Husky catalyst, is designated as：MxM1-x-HCS.
Further preferred as scheme, described step (1) the high temperature carburizing reagent time is 1～8h.
Further preferred as scheme, two kinds of transition metal described in described step (3) are all in the periodic table of elements
Fourth line, any two kinds in Cr, Mn, Fe, Co and Cu；Described salting liquid is solvable acetate or the nitrate of metal.Step
Suddenly the mass ratio between two described in (3) kind transition metal salt is 1:(1-4).
Further preferred as scheme, plasma reactor output voltage 3-9kV described in described step (3), spoke
Penetrate time 5-20min.
Further preferred as scheme, described step (4) roasting time is in 1-5h.
Described volatile organic matter VOCs, defines boiling point in 50 DEG C -250 DEG C of chemical combination according to the World Health Organization
Thing, under room temperature, saturated vapor pressure, more than 133.32Pa, is present in a type organic of in the air at normal temperatures in vapour form.Press
The difference of its chemical constitution, can be further divided into eight classes：Alkanes, aromatic hydrocarbons, alkenes, halohydrocarbon, esters, aldehydes, ketone and
Other.The main component of general volatile organic matter VOCs has：Hydro carbons, halogenated hydrocarbons, oxygen hydrocarbon and nitrogen hydrocarbon, it includes：Benzene homologues,
Organic chloride, freon series, organic ketone, amine, alcohol, ether, ester, acid and oil hydrocarbon compound etc..
The general principle of the present invention and being contemplated that：Step (1) obtains the porous charcoal of Large ratio surface by high-temperature calcination reaction
Carrier；Step (2) passes through H2Oxygen in the oxy radical on carbonization silkworm excrement surface is deviate from by roasting, improves the polarity of carrier surface,
Weaken the strong absorption affinity to water for the carrier；Step (3) passes through plasma resonance, and transition metal is loaded to carbonization silkworm excrement material
On material；Step (4) forms higher catalytic activity point position by high-temperature calcination, and then obtains under low concentration and high humidity environment
VOCs gas has the catalyst of high catalytic activity.
The invention has the advantages that：
1. the double transition metal base carbonization silkworm excrement catalyst obtained by the present invention, the carrier being used is through H2After roasting,
Content of surface oxygen is lower than the oxygen content of general commercialization activated carbon, can significantly improve the hydrophobicity of carrier surface, lifts catalyst
Overall hydrophobicity, weakens under high humidity environment, the significantly decline of the catalytic performance being led to due to hydrone competition.
2. obtained by the present invention catalyst after plasma resonance, the transition metal ions being loaded can be with carrier
Form stronger adhesion, weaken the obscission of carried metal during catalyst uses.
3. obtained by the present invention, catalyst carries out the load of active component by way of low temperature plasma radiates, and makes to urge
Change active component to generate within the extremely short time, therefore crystal grain is less, catalysis activity strengthens.
4. carrier used in the present invention is carbonization silkworm excrement, belongs to twice laid, wide material sources and with low cost, direct carbon
Change method completes, and process is simple and environmental protection；Meanwhile, the transition metal source cost being used is relatively low honest and clean, preparation process is simple, is suitable for
Large-scale industrial production.
Brief description
Fig. 1 is the SEM of double transition metal base carbonization silkworm excrement catalyst.
Fig. 2 is double catalytic degradation curve under different humidity for the transition metal base carbonization silkworm excrement catalyst.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and examples, but the scope of protection of present invention is not
It is confined to the scope of embodiment statement.
Embodiment 1
The preparation method of a kind of pair of transition metal carbonization base silkworm excrement catalyst, comprises the steps,
(1) preparation of carbonization base silkworm excrement
In N2In atmosphere, 10.0g Faeces bombycis are raised to 500 DEG C with the heating rate of 5 DEG C/min, and keep 3h at 500 DEG C
Cool to room temperature after above, obtain carbonization silkworm excrement, be designated as CS.
(2) H of carbonization base silkworm excrement2Deoxidation treatment
0.5g CS is placed in 10% (volume ratio) H2The N of concentration2Low oxygen containing carbon is obtained in 200 DEG C of roasting 1.0h under atmosphere
Change base silkworm excrement HCS；
(3) 0.3g copper nitrate and 0.3g ferric acetate are dissolved in 30ml deionized water, then 0.5g HCS be impregnated in
In their salting liquid, put into after drying in plasma reactor, be passed through N2As modified gas, plasma reactor
Output voltage 3kV, radiated time 20min, obtain Cu0.5Fe0.5-HCS1；
(4) roasting of catalyst：Cu0.5Fe0.5-HCS1Roasting 5h at 150 DEG C, finally obtains a kind of pair of transition metal base
Carbonization base silkworm excrement catalyst, is designated as：Cu0.5Fe0.5-HCS.
Embodiment 2
The preparation method of a kind of pair of transition metal base carbonization base silkworm excrement catalyst, comprises the steps,
(1) preparation of carbonization base silkworm excrement
In N2In atmosphere, 10.0g Faeces bombycis are raised to 600 DEG C with the heating rate of 2 DEG C/min, and keep 8h at 600 DEG C
After cool to room temperature, to carbonization silkworm excrement, be designated as CS.
(2) H of carbonization base silkworm excrement2Deoxidation treatment
0.5g CS is placed in 15% (volume ratio) H2The N of concentration2Low oxygen containing carbon is obtained in 300 DEG C of roasting 2.0h under atmosphere
Change base silkworm excrement HCS；
(3) 0.15g cobalt nitrate and 0.3g ferric acetate are dissolved in 30ml deionized water, then 0.2g HCS be impregnated in
In their salting liquid, put into after drying in plasma reactor, be passed through N2As modified gas, plasma reactor
Output voltage 6kV, radiated time 15min, obtain Co0.33Fe0.67-HCS1；
(4) roasting of catalyst：Co0.33Fe0.67-HCS1Roasting 4h at 250 DEG C, finally obtains a kind of pair of transition metal
Base carbonization silkworm excrement catalyst, is designated as：Co0.67Fe0.33-HCS.
Embodiment 3
The preparation method of a kind of pair of transition metal base carbonization silkworm excrement catalyst, comprises the steps,
(1) preparation of carbonization silkworm excrement
In N2In atmosphere, 10.0g Faeces bombycis are raised to 1000 DEG C with the heating rate of 8 DEG C/min, and keep at 1000 DEG C
Cool to room temperature after more than 1h, obtain carbonization silkworm excrement, be designated as CS.
(2) H of carbonization silkworm excrement2Deoxidation treatment
0.5g CS is placed in 20% (volume ratio) H2The N of concentration2Low oxygen containing carbon is obtained in 400 DEG C of roasting 3.0h under atmosphere
Change silkworm excrement HCS；
(3) 0.15g cobalt nitrate and 0.6g chromic nitrate are dissolved in 30ml deionized water, then 0.3g HCS be impregnated in
In their salting liquid, put into after drying in plasma reactor, be passed through N2As modified gas, plasma reactor
Output voltage 7kV, radiated time 10min, obtain Co0.25Cr0.75-HCS1；
(4) roasting of catalyst：Co0.25Cr0.75-HCS1Roasting 3h at 350 DEG C, finally obtains a kind of pair of transition metal
Base carbonization silkworm excrement catalyst, is designated as：Co0.25Cr0.75-HCS.
Embodiment 4
The preparation method of a kind of pair of transition metal base carbonization silkworm excrement catalyst, comprises the steps,
(1) preparation of carbonization silkworm excrement
In N2In atmosphere, 10.0g Faeces bombycis are raised to 700 DEG C with the heating rate of 4 DEG C/min, and keep 4h at 700 DEG C
Cool to room temperature after above, obtain carbonization silkworm excrement, be designated as CS.
(2) H of carbonization silkworm excrement2Deoxidation treatment
0.5g CS is placed in 25% (volume ratio) H2The N of concentration2Low oxygen containing carbon is obtained in 500 DEG C of roasting 4.0h under atmosphere
Change silkworm excrement HCS；
(3) 0.15g chromic nitrate and 0.3g manganese acetate are dissolved in 30ml deionized water, then 0.5g HCS be impregnated in
In their salting liquid, put into after drying in plasma reactor, be passed through N2As modified gas, plasma reactor
Output voltage 8kV, radiated time 8min, obtain Cr0.33Mn0.67-HCS1；
(4) roasting of catalyst：Cr0.33Mn0.67-HCS1Roasting 2h at 450 DEG C, finally obtains a kind of pair of transition metal
Base carbonization silkworm excrement catalyst, is designated as：Cr0.33Mn0.67-HCS.
Embodiment 5
The preparation method of a kind of pair of transition metal base carbonization silkworm excrement catalyst, comprises the steps,
(1) preparation of carbonization silkworm excrement
In N2In atmosphere, 10.0g Faeces bombycis are raised to 900 DEG C with the heating rate of 6 DEG C/min, and keep 2h at 900 DEG C
Cool to room temperature after above, obtain carbonization silkworm excrement, be designated as CS.
(2) H of carbonization silkworm excrement2Deoxidation treatment
0.5g CS is placed in 30% (volume ratio) H2The N of concentration2Low oxygen containing carbon is obtained in 350 DEG C of roasting 5.0h under atmosphere
Change silkworm excrement HCS；
(3) 0.3g manganese acetate and 0.3g cobalt nitrate are dissolved in 30ml deionized water, then 0.7g HCS be impregnated in
In their salting liquid, put into after drying in plasma reactor, be passed through N2As modified gas, plasma reactor
Output voltage 9kV, radiated time 5min, obtain Mn0.5Co0.5-HCS1；
(4) roasting of catalyst：Mn0.5Co0.5-HCS1Roasting 1h at 500 DEG C, finally obtains a kind of pair of transition metal base
Carbonization silkworm excrement catalyst, is designated as：Mn0.5Co0.5-HCS.
Material properties test：
(1) surface topography of double transition metal base carbonization silkworm excrement Pd/carbon catalysts
Embodiment 1 prepared by the present invention carries out electron-microscope scanning, obtains the SEM figure of Fig. 1.
From figure 1 it appears that the original wrinkled surface of silkworm excrement fades away, occur in that very abundant channel design,
Channel interior is coated with tiny crystal grain, presents multiple aperture duct net distribution general layout.The particle of photocatalyst crystals
Diameter is very regular, is about distributed between 100-200nm.
(2) pore structure parameter of double transition metal base carbonization silkworm excrement catalyst and Elemental redistribution
The ASAP-2020 specific surface pore-size distribution instrument being produced using Micro company of the U.S. is to five samples of embodiment
Pore structure is characterized, and result is as shown in table 1.Five kinds of prepared materials, their Langmuir specific surface area about exists
400-650m2The specific surface area that/g, wherein micropore (aperture is less than 2nm) are accounted for is about in 189-254m2/g.Their total hole
Hold in 0.11-0.26cm3In/g range.Compared with unsupported bimetallic CS material, specific surface and pore volume all have to a certain degree
Decline, this explanation bimetallic oxide occupy certain specific surface area so that the hole number of micropore and mesopore has reduced.
The specific surface area of the double transition metal base carbonization silkworm excrement catalyst of 1. 5 kinds of embodiment gained of table and pore volume
Table 2 shows metal and the O element mass content of five kinds of embodiment samples.It can be seen that in material
Oxygen content be less than 8%, containing total metal content between 5-15%, and the ratio of mol ratio and added slaine very close to.
Table 2 is metal and the oxygen element content of embodiment 1-5
Fig. 2 shows in 293K and drying and relative humidity<(toluene concentration is 200ppm), first under the conditions of 10% and 80%
Catalytic degradation curve on embodiment 3 resulting materials for the benzene.It can be seen that humidity degraded to toluene to embodiment 3
Influential effect is less, the temperature T when degradation rate of its toluene is more than 90%90For 287 DEG C, than T during relative humidity 80%90High
10-13℃.This shows that obtained material has good catalytic effect at high humidity.
Table 3 shows the effect that five kinds of samples of inventive embodiments are degraded to low concentration VOCs, from table 3 it can be seen that relatively
Under low VOCs concentration, obtained material T90Temperature all relatively low, and affected by humidity to the catalysis degradation modulus of VOCs
Less, show preferable hydrophobicity.
The effect that table five kinds of samples of 3 embodiment of the present invention are degraded to low concentration VOCs
Claims (9)
1. a kind of pair of transition metal base carbonization silkworm excrement catalyst it is characterised in that：Described double transition metal base carbonization silkworm excrements are urged
The oxygen content of the catalyst carrier carbonization silkworm excrement of agent<8.0wt%, the content summation of transition metal is in 5-15wt%；Described
Double transition metal base carbonization silkworm excrement catalyst, the BET specific surface area having is 400-650m2/g.
2. as claimed in claim 1 double transition metal base carbonization silkworm excrement catalyst preparation method it is characterised in that：Including such as
Lower step,
(1) preparation of carbonization silkworm excrement CS：Silkworm excrement is placed in high temperature process furnances, after logical protective gas purging, it is heated to 500～
1000 DEG C carry out high temperature cabonization reaction and obtain carbonization silkworm excrement, are designated as CS；
(2) H of carbonization silkworm excrement2Deoxidation treatment：CS is placed in containing H2N2Under atmosphere, obtain low in 200-500 DEG C of roasting 1-5h
Oxygen containing carbonization silkworm excrement HCS；
(3) HCS be impregnated in the salting liquid of two kinds of transition metal, by transition by way of plasma resonance after drying
Metal Supported on HCS, prepared MxM1-x-HCS1；
(4) roasting of catalyst：MxM1-x-HCS1Roasting at 150-500 DEG C, finally obtains double transition metal base carbonization silkworm excrements and urges
Agent, is designated as：MxM1-x-HCS.
3. according to claim 2 pair of transition metal base carbonization silkworm excrement catalyst preparation method it is characterised in that：Described
Step (1) the high temperature carburizing reagent time is 1～8h.
4. according to claim 2 pair of transition metal base carbonization silkworm excrement catalyst preparation method it is characterised in that：Step
(2) H in2In N2Volume ratio in atmosphere is 10-30%.
5. according to claim 2 pair of transition metal base carbonization silkworm excrement catalyst preparation method it is characterised in that：Step
(3) two described in kind transition metal is any two kinds in Cr, Mn, Fe, Co and Cu；Described salting liquid is the solvable of metal
Acetate or nitrate.
6. according to claim 2 pair of transition metal base carbonization silkworm excrement catalyst preparation method it is characterised in that：Step
(3) 3-9kV of plasma reactor output voltage described in, radiated time 5-20min.
7. according to claim 2 pair of transition metal base carbonization silkworm excrement catalyst preparation method it is characterised in that：Step
(3) mass ratio between two described in kind transition metal salt is 1:1-4.
8. according to claim 2 pair of transition metal base carbonization silkworm excrement catalyst preparation method it is characterised in that：Step
(4) roasting time is in 1-5h.
9. the application of double transition metal base carbonization silkworm excrement catalyst is obtained as claimed in claim 1 it is characterised in that：It is being waved
The catalytic degradation aspect application of the property sent out organic matter VOCs.
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